U.S. patent number 3,750,907 [Application Number 05/026,604] was granted by the patent office on 1973-08-07 for fluid containers having both relatively strong and relatively weak seals.
This patent grant is currently assigned to Eastman Kodak Company. Invention is credited to John D. Steele.
United States Patent |
3,750,907 |
Steele |
August 7, 1973 |
FLUID CONTAINERS HAVING BOTH RELATIVELY STRONG AND RELATIVELY WEAK
SEALS
Abstract
A fluid container or pod for photographic processing liquid
having a pair of walls carrying a heat activatable adhesive sealed
together marginally by heat sealing. Preferably the container walls
are both flexible and comprise lead foil carrying kraft paper on
one side; and carrying on the other side a coating of a synthetic
resin upon which is coated the heat activatable adhesive. The heat
activatable adhesive is selected from the group consisting of (a) a
plurality of mixed polymers, and (b) a mixture of a polymer
selected from the group consisting of alcohol-soluble cellulose
acetate butyrate, a polyhydroxy ether resulting from
copolymerization of bisphenol A with epichlorohydrin, and
toluene-soluble cellulose acetate butyrate, with a plasticizer
selected from the group consisting of triphenyl phosphate and
sulfonamide-formaldehyde resin. By varying the temperature,
pressure and time in heat sealing, selected portions of the seal
can be relatively strong, and other selected portions relatively
weak, for controlled release of liquid through the weak seal
portions when pressure is applied.
Inventors: |
Steele; John D. (Columbia,
SC) |
Assignee: |
Eastman Kodak Company
(Rochester, NY)
|
Family
ID: |
21832768 |
Appl.
No.: |
05/026,604 |
Filed: |
April 8, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
835420 |
Jun 23, 1969 |
|
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|
|
Current U.S.
Class: |
222/107;
206/484.2; 206/524.2; 383/210; 430/496; 524/141 |
Current CPC
Class: |
B32B
15/08 (20130101); C08L 63/00 (20130101); C09J
163/00 (20130101); B32B 27/00 (20130101); C08L
63/00 (20130101); B65D 75/26 (20130101); C09J
163/00 (20130101); C08L 2666/02 (20130101); C08L
2666/26 (20130101); C08L 2666/02 (20130101) |
Current International
Class: |
B32B
15/08 (20060101); B32B 27/00 (20060101); B65D
65/40 (20060101); B65D 75/26 (20060101); C08L
63/00 (20060101); C09J 163/02 (20060101); C08L
63/02 (20060101); B65d 035/08 (); B65d 035/14 ();
B65d 035/16 () |
Field of
Search: |
;96/29,76 ;222/107 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Torchin; Norman G.
Assistant Examiner: Goodrow; John L.
Parent Case Text
This application is a continuation-in-part of my application Ser.
No. 835,420 which was filed June 23, 1969, now abandoned.
Claims
I claim:
1. A fluid container for photographic processing liquid having a
pair of opposed walls marginally sealed together over a substantial
sealing area to provide a liquid retaining cavity, at least one of
said walls being flexible and deformable, said opposed walls over
the entire internal areas thereof having a processing liquid
resistant polymeric resin underlayer, and over at least said entire
sealing area both walls having the same coating over said
underlayer of a chemical composition comprising at least one
thermoplastic polymer, the coatings of said walls being heat sealed
together, a selected part of said area having been subjected to one
set of temperature, pressure, and time conditions to form a
relatively strong seal, another part of said area having been
subjected to a different set of such conditions to form a
relatively weaker seal, whereby upon application of pressure to
said container only said weaker seal ruptures and releases said
liquid, said coating being selected from the group consisting of
(a) a mixture of two polymers, the first one of said polymers being
selected from the group consisting of cellulose nitrate and alcohol
soluble cellulose acetate butyrate, the second one of said polymers
being selected from the group consisting of styrene-methyl
methacrylate copolymer, toluene soluble cellulose acetate butyrate,
and polyvinyl butyral, and (b) a mixture of a polymer selected from
the group consisting of alcohol soluble cellulose acetate butyrate,
a polyhydroxy ether resulting from copolymerization of bisphenol A
with epichlorohydrin, and toluene soluble cellulose acetate
butyrate, with a plasticizer selected from the group consisting of
triphenyl phosphate and sulfonamide-formaldehyde resin.
2. A fluid container in accordance with claim 1 wherein said walls
at least over the marginally sealed area thereof have a heat
sealable coating comprising such an intimate mixture of two
polymers, said first one of said polymers being characterized by
inherent relatively weak heat sealability, said second one of said
polymers being characterized by inherent relatively strong heat
sealability.
3. A fluid container in accordance with claim 2 wherein said first
polymer is selected from the group consisting of cellulose nitrate
and alcohol soluble cellulose acetate butyrate, and wherein said
second polymer is selected from the group consisting of
styrene-methyl methacrylate copolymer, toluene soluble cellulose
acetate butyrate, and polyvinyl butyral.
4. A fluid container in accordance with claim 3 wherein said first
and second polymers are present in a ratio between 4 to 1 and 1 to
4 by weight.
5. A fluid container in accordance with claim 4 wherein said
mixture consists essentially of styrene-methyl methacrylate
copolymer and alcohol soluble cellulose acetate butyrate.
6. A fluid container in accordance with claim 4 wherein said
mixture consists essentially of toluene soluble cellulose acetate
butyrate and alcohol soluble cellulose acetate butyrate.
7. A fluid container in accordance with claim 4 wherein said
mixture consists essentially of polyvinyl butyral and alcohol
soluble cellulose acetate butyrate.
8. A fluid container in accordance with claim 4 wherein said
mixture consists essentially of polyvinyl butyral and cellulose
nitrate.
9. A fluid container in accordance with claim 1 wherein said walls
at least over the marginally sealed areas thereof have a heat
sealable coating comprising such an intimate mixture of a
thermoplastic polymer selected from the group consisting of alcohol
soluble cellulose acetate butyrate, toluene soluble cellulose
acetate butyrate, and a polyhydroxy ether resulting from
copolymerization of bisphenol A with epichlorohydrin; and a
plasticizer selected from the group consisting of triphenyl
phosphate and sulfonamide-formaldehyde resin; said misture being
characterized by the ability to form a relatively strong seal when
subjected to one set of conditions of temperature, pressure and
time, and to form a relatively weaker seal when subjected to a
different set of conditions.
10. A fluid container in accordance with claim 9 wherein said
thermoplastic polymer is alcohol soluble cellulose acetate
butyrate, and wherein said plasticizer is sulfonamide-formaldehyde
resin.
11. A fluid container in accordance with claim 9 wherein said
thermoplastic polymer is alcohol soluble cellulose acetate
butyrate, and wherein said plasticizer is triphenyl phosphate.
12. A fluid container in accordance with claim 9 wherein said
thermoplastic polymer is a polyhydroxy ether resulting from
copolymerization of bisphenol A with epichlorohydrin, and wherein
said plasticizer is sulfonamide-formaldehyde resin.
13. A fluid container in accordance with claim 9 wherein said
thermoplastic polymer is a polyhydroxy ether resulting from
copolymerization of bisphenol A with epichlorohydrin, and wherein
said plasticizer is triphenyl phosphate.
14. A fluid container in accordance with claim 9 wherein said
thermoplastic polymer is toluene soluble cellulose acetate
butyrate, and wherein said plasticizer is triphenyl phosphate.
15. A method of forming a fluid container in accordance with claim
1, comprising providing a pair of opposed walls having the entire
internal areas thereof provided with an underlayer of heat sealable
resin and over at least marginal areas thereof on top of said
underlayer an overcoating of a chemical composition comprising at
least one thermoplastic polymer, said composition being selected
from the group consisting of (a) a mixture of two polymers, the
first one of said polymers being selected from the group consisting
of cellulose nitrate and alcohol soluble cellulose acetate
butyrate, the second one of said polymers being selected from the
group consisting of styrene-methyl methacrylate copolymer, toluene
soluble cellulose acetate butyrate, and polyvinyl butyrate, said
first one of said polymers being characterized by inherent
relatively weak heat sealability, said second one of said polymers
being characterized by inherent relatively stronger heat
sealability; and (b) a mixture of a polymer selected from the group
consisting of alcohol soluble cellulose acetate butyrate, a
polyhydroxy ether resulting from copolymerization of bisphenol A
with epichlorohydrin, and toluene soluble cellulose acetate
butyrate, with a plasticizer selected from the group consisting of
triphenyl phosphate and sulfonamide-formaldehyde resin;
placing said opposed walls together over said marginal areas;
subjecting a first part of said marginal areas to one set of
conditions of temperature, pressure, and time to form a relatively
strong seal; and
subjecting another part of said marginal areas to a different set
of conditions of temperature, pressure, and time effective to form
a relatively weaker seal, whereby liquid is releasable through said
weaker seal upon application of pressure to said container.
16. A method in accordance with claim 15 wherein said composition
comprises said first polymer selected from the group consisting of
cellulose nitrate and alcohol soluble cellulose acetate butyrate,
and said second polymer selected from the group consisting of
styrene-methyl methacrylate copolymer, toluene soluble cellulose
acetate butyrate, and polyvinyl butyral.
17. A method in accordance with claim 15 wherein said composition
comprises a polymer selected from the group consisting of alcohol
soluble cellulose acetate butyrate, toluene soluble cellulose
acetate butyrate, and a polyhydroxy ether resulting from
copolymerization of bisphenol A with epichlorohydrin; and a
plasticizer selected from the group consisting of triphenyl
phosphate and sulfonamide-formaldehyde resin.
18. A method in accordance with claim 15, also comprising providing
said coating by dissolving the selected composition in a solvent,
coating the resulting solution on said areas, and permitting said
solvent to evaporate.
19. A method in accordance with claim 15, wherein said first part
of said area is sealed at a temperature between 200.degree. and
400.degree. F., and said other part of said area is sealed at a
lower temperature between 150.degree. and 350.degree. F.
20. A fluid container in accordance with claim 1 wherein said
selected part of said area having a relatively strong seal
comprises two opposite sides of said fluid container, and wherein
said other part of said area comprises the other two opposite
sides, said other two opposite sides being sealed with seals of
essentially the same relatively weaker strength.
21. A fluid container in accordance with claim 1 wherein said walls
comprise a plurality of layers, one of said layers being lead foil,
another of said layers being kraft paper adhering to the outside of
said lead foil, and another of said layers being a polymeric resin
adhering to the inside of said lead foil between said lead foil and
said coating.
22. A fluid container in accordance with claim 5 wherein said walls
comprise a plurality of layers, one of said layers being lead foil,
another of said layers being kraft paper adhering to the outside of
said lead foil, and another of said layers being a polymeric resin
adhering to the inside of said lead foil between said lead foil and
said coating.
23. A fluid container in accordance with claim 9 wherein said walls
comprise a plurality of layers, one of said layers being lead foil,
another of said layers being kraft paper adhering to the outside of
said lead foil, and another of said layers being a polymeric resin
adhering to the inside of said lead foil between said lead foil and
said coating.
24. A method in accordance with claim 19 wherein said composition
consists essentially of alcohol soluble cellulose acetate butyrate
and styrene-methyl methacrylate copolymer in a ratio between 4 to 1
and 1 to 4 by weight.
25. A container in accordance with claim 22 filled with an alkaline
photographic processing solution.
26. A fluid container for photographic processing liquid having a
pair of opposed walls marginally sealed together over a substantial
sealing area to provide a liquid retaining cavity, at least one of
said walls being flexible and deformable, said opposed walls over
the entire internal areas thereof each having a processing
liquid-resistant thermoplastic polymeric vinyl resin layer;
said opposed walls over at least a marginal area thereof each
having a coating over said vinyl resin layer of a mixture of
alcohol soluble cellulose acetate butyrate and styrene-methyl
methacrylate copolymer in a ratio between 4 to 1 and 1 to 4 by
weight;
part of said sealing area comprising a relatively strong seal
comprising vinyl resin of said layers fused together, the remainder
of said sealing area comprising a relatively weaker seal comprising
only said coatings fused together.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to fluid containers which are
particularly adapted to retain photographic processing
compositions. More particularly, the invention concerns such
containers, and a method for making same, so constructed that a
relatively weak seal is provided where the photographic processing
composition is to be released, and a relatively stronger seal is
provided over other parts of the container where necessary to
prevent release.
2. The Prior Art
U.S. Pat. No. 3,173,580 relates to fluid containers for
photographic processing compositions which are formed of a
plurality of layers comprising, respectively, an outer layer of
kraft paper, a layer of metal foil, and an inner layer of a
thermoplastic resin comprising polyvinyl chloride. The containers
there described are sealed by the application of heat to marginal
areas so as to unite the polyvinyl chloride layers without the use
of an adhesive composition. A weak seal on the edge where the
photographic composition is to be released is secured by heating
appropriate marginal areas under mechanical pressure and at a
temperature substantially lower than the temperature to which the
remaining portions of the marginally sealed areas are
subjected.
SUMMARY OF THE INVENTION
In accordance with the present invention, there is provided a novel
fluid container for photographic processing compositions having a
pair of opposed walls marginally sealed together face to face, over
a substantial area to provide a liquid retaining cavity. At least
one, and preferably both, of the walls are flexible and deformable,
preferably comprising a sheet of lead foil carrying on the side
facing the cavity a layer or coating of a synthetic polymeric resin
upon which is coated a heat activatable adhesive on at least the
marginal areas to be sealed; and carrying kraft paper on the
opposite side.
The layer of polymeric resin is one which is resistant to the
liquid within the container and capable of forming a heat seal, and
advantageously extends over the entire internal area of each
wall.
The adhesive is present as a thin coating of a chemical composition
comprising at least one thermoplastic polymer other than polyvinyl
chloride, and should be selected from (a) a plurality of mixed
polymers, and (b) a polymer selected from the group consisting of
alcohol soluble cellulose acetate butyrate, a polyhydroxy ether
resulting from copolymerization of bisphenol A with
epichlorohydrin, and toluene-soluble cellulose acetate butyrate,
mixed with a plasticizer selected from the group consisting of
triphenyl phosphate and sulfonamide-formaldehyde resin (a sulfonic
acid derivative) sold as MHP Santolite by Monsanto Company. The
adhesive coating can cover the entire areas defining the inner
walls of the container; or it can be coated only on marginal areas
where the seals are to be obtained, while the remaining areas are
coated with other compositions which will resist the photographic
chemicals.
When using this construction improved controlled strength of the
seal is secured by varying the temperature, pressure and time of
heat sealing at selected parts of the sealed areas. With high
temperatures, and/or high pressures strong seals are provided which
will withstand force values such as greater than 1,000 grams and
thus will not burst when the container is compressed. Such a strong
seal is believed to result from resin punching through the thin
adhesive coating in numerous spots. On the other hand, using lower
temperatures and/or pressures, only the thin adhesive coatings are
believed to unite and the area sealed is weaker than the other
areas sealed at higher temperatures and/or pressures, and tends to
open up at a force value between 10 and 1,000 grams when the
container is compressed, so that the contents can be discharged and
distributed uniformly over a selected area of a photographic
element to be processed.
My containers resist deterioration in the presence of photographic
solutions, such as caustic alkali and/or organic
nitrogen-containing compounds of the type employed in the
processing of silver halide photographic emulsions.
THE DRAWINGS
The invention will be described with reference to the drawings
wherein:
FIG. 1 is a perspective view showing schematically the appearance
of one type of fluid container contemplated by the invention;
FIG. 2 is a cross sectional view taken along the line 2--2 in FIG.
1;
FIG. 3 is a perspective view showing schematically a blank having a
center fold for making up a modified form of container embodying
the invention;
FIG. 4 is a cross sectional view taken along the line 4--4 in FIG.
5;
FIG. 5 is a plan view of the container shown in FIG. 4 formed by
folding the blank of FIG. 3 and heat sealing the marginal
areas;
FIG. 6 is a perspective view of a sheet of laminated material for
forming the containers of FIGS. 1-5;
FIG. 7 is a perspective view of another sheet of laminated material
adapted to be formed into a container; and
FIG. 8 is a schematic sectional view, partly in elevation, showing
how the container is used in a camera.
THE PREFERRED EMBODIMENTS
Sometimes it is necessary to apply a small quantity of liquid
material in a thin layer over a fairly large surface within a piece
of apparatus, such as a camera, without gaining access to the
interior of the apparatus. For example, a photosensitive film may
be processed or a photograph may be toned by applying on the
surface thereof within a camera a layer of a liquid processing
reagent, such as a developer for a silver-halide emulsion, or a
solution of a toning agent. The present invention makes it possible
to apply such a thin layer by incorporating within the apparatus a
disposable fluid container in the form of a pod or pouch having at
least one wall which is formed of a flexible compressible material,
and having sealed areas which are relatively weak at one part and
relatively stronger at another part for selective opening of the
weak seal when the wall is compressed. With this construction, the
container wall can be compressed by an internal mechanical device,
whereupon the liquid contained within the container is expelled
uniformly through the opened weak seal in the desired direction
onto the surface area to be coated.
It is particularly important that such containers be so constructed
as to resist deterioration in storage as the result of chemical
action by the contained liquids. Deterioration of the container not
only may cause leakage from the container, but also may cause
contamination of the contained fluid.
The principles of the invention depend primarily upon the use of
novel sealing compositions which react to the application of heat
and pressure to marginal areas in such a way that variations in
these conditions, and in time, result in seals of different
strengths. The particular novel compositions will be described more
in detail hereinafter, but first the mechanical construction of
containers utilizing the invention will be described with reference
to the drawings.
FIG. 1 shows a container C comprising an upper wall 11 and a lower
wall 12, both of flexible material, which are sealed together along
marginal areas 13 extending completely around all four sides of the
container. The internal areas of the container walls are not sealed
together, but are spaced apart to form a storage space for liquid
in the form of a bubble-like protuberance 14 on each side of the
container.
Now, referring to FIG. 2, the two flexible walls 11 and 12 are of
laminated construction and include several layers which are
adhesively joined. Specifically layers 15 of strong kraft paper are
adhered to layers 17 of metal foil, such as lead or aluminum which
is impervious to the passage of liquid and to the passage of air
from the outside into the liquid. Such paper-foil laminates are
generally purchased in sheet form as they are readily available on
the market.
Layers 19 are a polymeric resinous material which is resistant to
the action of the contained liquid, such as a copolymer of vinyl
chloride with 2-15 percent by weight of vinyl acetate. This layer
is adhered to the lead foil by a sub such as described in my
abandoned application Ser. No. 835,353, filed June 23, 1969,
entitled "Fluid Containers Resistant to Photographic Processing
Solutions," now pending as Ser. No. 26,605 (a
continuation-in-part), the disclosure of which is incorporated by
reference. A final layer 21 is the novel sealing composition of the
present invention.
The two halves 11 and 12 of the container are joined together along
marginal portions 13 by heat sealing at one set of conditions of
temperature, pressure and time for a strong seal on two or three of
the sides, and a different set of such conditions to produce a weak
seal 23 on the remaining side or sides. When the liquid is to be
expelled through weak seal 23 by passing a pair of rolls over the
container, the nip of the rolls can be positioned at the back side
24 and moved toward the front side 23 to expel the liquid at 23.
Success is achieved when the seal at side 24 is stronger, weaker,
or the same as seal 23, as long as the seals at sides 26 and 28 are
enough stronger than seal 23 to resist bursting. In fact, side 24
need not be sealed at all for operability, although it should be
sealed for storage purposes. When seals at 23 and 24 are of equal
strength, the container or pod can be positioned with either side
forward for ease in assembly of film packs or rolls.
In FIG. 2 the sealing layers 21 extend over the entire internal
surfaces of the walls 11 and 12, but are only sealed together
marginally. A pool 25 of photographic processing liquid inside
container C will be expelled when the container is compressed and
weak seal 23 is opened while the other edges remain sealed.
FIGS. 3-5 show a different construction wherein a container C' is
formed by folding a rectangular blank 29 along a median line 30,
and then sealing together the two end margins 31 and 33 with a
relatively strong seal and the long side margin 35 with a
relatively weaker seal for the discharge of liquid from the
container when pressure is applied to the container sufficient to
break the weak seal 35.
Referring to FIG. 4, even though the side 37 of the container is
closed inherently, it is desirable to heat seal the adjoining areas
together so as to form that side with a streamline design to make
it easy to pass across the container a pair of compressing rollers
or similar compressing devices.
The laminated sheet from which the container C' is made is like
that described in connection with FIG. 2, and is further shown on a
somewhat larger scale in FIG. 6 wherein 15' is kraft paper, 17' is
lead, 19' is polyvinyl chloride-polyvinyl acetate copolymer, and
21' is the sealing layer of the invention. The paper and the
polyvinyl chloride-polyvinyl acetate copolymer layers may be joined
to the lead layer by using a suitable adhesive material. The
sealing layer 21' can be joined to the layer of polyvinyl
chloride-polyvinyl acetate copolymer by the use of an intermediate
adhesive when layer 21' is in sheet form; or by applying the
material of layer 21' in solution in an organic solvent and
permitting the solvent to evaporate.
In FIG. 7 there is shown a sheet of material that can be formed
into a container, but without the entire inner surface of the
container being coated with the sealing layer of the invention. The
FIG. 7 modification is a laminated sheet having a paper layer 15",
a foil layer 17", and a polyvinyl chloride-polyvinyl acetate
copolymer layer 19" joined to the foil by an adhesive sub 20".
Instead of coating the entire surface of layer 19" with the
composition of the invention, coating is only applied to two narrow
marginal areas 39 and 41 extending longitudinally of the sheet, and
to a series of longitudinally spaced transverse narrow areas 43 and
45. When forming the sheet C" into containers, transverse cuts are
made centrally through the areas 43 and 45, and the blanks thus
formed are folded along a transverse fold line midway between areas
43 and 45, as described in connection with FIGS. 3-5. Alternately,
after cutting, two blanks can be positioned face-to-face and heat
sealed in the manner described in connection with FIGS. 1 and 2.
Heat sealing of the two end and one side marginal areas is then
accomplished, but the contained liquid is only in contact with the
polyvinyl chloride-polyvinyl acetate copolymer layer 19" bounded by
the marginal areas. Strong and weak seals are assured in the same
way described in connection with the other figures.
Instead of sealing the entire lengths of edges 23 and 35 under
conditions to form a weak seal, it sometimes is desirable to
provide alternate areas of weak and strong sealing to assure
uniform distribution of the liquid contents. For example, two areas
of weak sealing may be provided, spaced apart by a central or
intermediate area of strong sealing whereby the liquid is ejected
in two separate streams which merge subsequently.
FIRST MODIFICATION OF SEALING COMPOSITION
The novel compositions for the heat seal layers will now be
described in detail. In one type of composition the heat sealable
layer is an intimate mixture of two polymeric resins, one of which
is characterized by inherent relatively weak heat sealability, and
the other of which is characterized by inherent relatively stronger
heat sealability. This mixture of polymers is formed in a suitable
mutual organic solvent which is compatible with both polymers, the
resulting solution is uniformly coated on the areas desired, and
the solvent is permitted to evaporate. The organic solvent can be
tetrahydrofuran, methyl ethyl ketone, methyl alcohol, ethyl
alcohol, or chlorinated hydrocarbon solvents such as
dichlormethane. Ratios between 4:1 and 1:4 by weight are operable,
but narrower ranges may be preferred. When the solvent has
evaporated, small microscopic islands or particles of each polymer
individually form in the seal layer. Sealing then takes place
between the islands of relatively strong seal polymer, which soften
at a lower temperature than do the islands of relatively weak seal
polymer. Examples of suitable compositions of mixed polymers are as
follows:
TABLE I
A. Relatively B. Relatively Ratio Strong Seal Polymer Weak Seal
Polymer A/B 1. Styrene-methylmethacrylate Alcohol soluble 4:1 to
1:4 copolymer cellulose acetate (Zerlon 150-Dow Chemical butyrate
(ASB- Co. or Richardson R 570- Tennessee Eastman) Richardson Co.)
(soften at (softens at higher about 205.degree.F.) than
205.degree.F.) 2. Toluene soluble cellulose " 3:1 to 1:3 acetate
butyrate (EAB 381-Tennessee Eastman 3. Polyvinyl butyral Alcohol
soluble 3:1 to 1:3 (Butvar B-76-Monsanto) cellulose acetate
butyrate (ASB- Tennessee Eastman) (softens at higher than
205.degree.F.) 4. " Cellulose nitrate 3:1 to 1:3
In the foregoing compositions the particular cellulose acetate
butyrate of composition No. 2 (EAB 381) is toluene soluble and
alcohol insoluble; is characterized by having 12-15 percent acetyl,
more than 20 percent (advantageously 35-39 percent) butyryl, and
1.6-1.8 percent free hydroxyl; and has an average molecular weight
of about 40,000. Success may be achieved when this composition has
an intrinsic viscosity in acetone of between 0.7 and 1.85.
The Butvar B-76 resin of composition No. 3 is a commercial
poly(vinyl butyral) having a hydroxyl content expressed as percent
poly(vinyl alcohol) of between 9 and 13, produced by Monsanto
Company.
The ASB alcohol soluble cellulose acetate butyrate of composition
No. 1 is described in U.S. Pat. No. 3,370,025 and is a resin which
is soluble in at least 95 percent anhydrous ethanol and is
characterized by 42-52 percent butyryl, less than 5 percent acetyl,
and 3-9 percent free hydroxyl (advantageously 48 percent, 2.8
percent, and 3 percent, respectively.)
Zerlon 150 is a copolymer containing, by weight, about 70 percent
methyl methacrylate and 30 percent styrene. Richardson R 570 is a
copolymer containing about 40 percent methyl methacrylate and 60
percent styrene. An operable range is from about 30 percent to
about 80 percent by weight of methyl methacrylate, balance
styrene.
Successful coatings of the compositions described above on a
substrate such as a laminated sheet have been secured with
solutions having the following compositions:
TABLE II
% by weight 1. Zerlon 150 1.8 ASB 1.2 Tetrahydrofuran or Methyl
Ethyl Ketone 97.0 2. Eab 381 3.5 ASB 1.5 Dichlormethane 94.0 Methyl
Alcohol 1.0 3. Butvar B-76 3.5 ASB 1.5 Ethyl Alcohol 95.0 4. Butvar
B-76 3.5 Cellulose Nitrate 1.5 Ethyl Alcohol 95.0
A heat seal temperature to form a relatively weak seal with the
above compositions should be selected within the range between
150.degree. and 350.degree. F.; and to form the relatively strong
seal a higher temperature should be selected within the range
between 200.degree. and 400.degree. F. Pressures may be varied
between 10 psi. and 3,000 psi, and the higher the pressure the
stronger is the seal (probably as a result of forcing the
underlying vinyl resin to punch through the seal layer and fuse
together). Dwell time for sealing may vary between 0.1 second and 3
seconds.
Generally the proper seal temperature is assured by the proper
temperatures of the sealing jaws or plates, within the above
ranges. In some cases the jaw temperature for the strong seal can
be no higher than, and even lower than, the jaw temperature for the
weak seal, as when the weak seal is made first and there is
residual heat left in the container. This can also be true when the
pressure exerted to produce the strong seals is substantially
greater than the pressure for the weak seals. Selection of the
proper temperature is accomplished by trial-and-error procedure.
Heating may be by conduction or induction, or may be by ultrasonic
vibrations, as described in Bodine U.S. Pat. No. 3,022,814 and many
others. Generation of the appropriate temperature ultrasonically is
accomplished by varying the vibration time, determined
empirically.
The force required to peel the seals apart varies between 3 and 100
grams for a weak seal, and 500 grams and up for a strong seal.
The polymer combinations described above produce the most stable
seals of all systems tested. Photographic developer liquid is kept
in containers using these polymer combinations as the internal
surfaces at 30.degree. to 150.degree. F., and at relative
humidities of 0 to 90 percent, with no damage to or deterioration
of the seal strength of the seals or the character of the developer
liquid.
While it is not fully understood how the combined resins operate to
achieve the beneficial results of this invention, theoretically it
is because the strong sealing occurs at the higher temperature
and/or higher pressure which causes the surface layer to be pushed
aside (or piled up) so that the underlying vinyl resin layer 19,
19' or 19" punches through the surface layer. Thus the vinyl resin
is exposed and fuses together to form a strong vinyl-to-vinyl seal.
On the other hand, the weak sealing occurs at the lower temperature
and/or pressure as a result of the fusing together of only that
portion of the surface sealing layer 21, 21', 41 which softens
first, while the rest of the sealing layer remains unfused, so that
the polymer mixtures provide microscopic points of sealing and
nonsealing.
SECOND MODIFICATION OF SEALING COMPOSITION
In a second modification of the invention, the heat sealing layer
or coating comprises an intimate mixture of a thermoplastic
polymeric resin selected from the group consisting of alcohol
soluble cellulose acetate butyrate, toluene soluble cellulose
acetate butyrate, and a polyhydroxy ether resulting from
copolymerization of bisphenol A with epichlorohydrin, with a
plasticizer selected from the group consisting of triphenyl
phosphate and MHP Santolite sulfonamide-formaldehyde resin. The
plasticizer combines with the polymer to reduce the heat seal
temperature, and makes it possible to control the degree of heat
sealing. Advantageously, 1 part of plasticizer by weight should be
present for between 10 and 30 parts by weight of resin.
Specific examples of compositions of this type which are
characterized by the ability to form selectively a relatively
strong or a relatively weak seal when subjected to different
conditions of temperature, pressure and time after being coated
upon the container walls from a solvent solution are as
follows:
TABLE III
% by weight 5. Alcohol soluble cellulose acetate 4 butyrate
(ASB-Tennessee Eastman) Sulfonamide-formaldehyde resin (MHP
Santolite-Monsanto) 0.16 Tetrahydrofuran 95.84 6. Alcohol soluble
cellulose acetate butyrate (ASB) 4 Triphenyl phosphate 0.16
Tetrahydrofuran 95.84 7. Polyhydroxy ether (phenoxy PK HH- Union
Carbide) 3.99 Sulfonamide-formaldehyde resin (MHP
Santolite-Monsanto) 0.32 Tetrahydrofuran 95.69 8. Polyhydroxy ether
(Phenoxy PK HH) 4.00 Triphenyl phosphate 0.16 Tetrahydrofuran 95.84
9. Toluene soluble cellulose acetate 3.99 butyrate (M 16
Lint-Tennessee Eastman) Triphenyl phosphate 0.16 Tetrahydrofuran
95.85
Further identification of those materials in Nos. 5-9 above which
have not been identified previously herein are as follows:
Phenoxy PK HH, sold by Union Carbide Corporation, is a high
molecular weight (about 30,000) polyhydroxy ether made by
copolymerizing bisphenol A and epichlorohydrin. The repeating unit
is: ##SPC1##
M 16 Lint, sold by Tennessee Eastman Company, is a toluene soluble
cellulose acetate butyrate essentially the same as EAB 381
described above.
Using the above combinations of polymeric resins and plasticizers,
the comments concerning the first modification also apply. Thus the
heat seal temperature required to form relatively weak seals should
be selected from the range between 150.degree. and 350.degree. F.,
and to form the relatively strong seals a higher temperature should
be selected between 200.degree. and 400.degree. F. Pressures can be
varied from 10 psi. to 3,000 psi., and the higher the pressure the
stronger is the seal; and the time of sealing can be varied between
0.1 second and 3 seconds. Under the conditions described the force
required to break the seals varies from 3 grams to 100 grams for a
weak seal, and 500 grams and higher for a strong seal.
In both modifications described in detail above, the coating 21,
21' or 41 advantageously is between 0.005 and 0.3 mil thick for
satisfactory results.
The underlayer 19, 19' or 19" of polymeric resin which is resistant
to the contained liquid and capable of forming a heat seal can be a
copolymer of polyvinyl chloride and polyvinyl acetate, a polyvinyl
acetal such as mentioned in U.S. Pat. No. 3,173,580, or other
polymeric resins such as nylon, polysulfones, and polyethylene.
My copending application has been referred to above for a
description of a sub layer that can be used for adhering the resin
coatings 19, 19' or 19" to the lead foil 17, 17' or 17".
Advantageously, such a sub layer comprises a thin coating of a
butadiene-acrylonitrile copolymer containing free carboxylic groups
(such as is produced by the B.F. Goodrich Chemical Co. and sold
under the trademark Hycar 1072, containing about 67 percent
butadiene, desirably 60-70 percent, and about 33 percent
acrylonitrile, desirably 30-40 percent by weight).
An even tighter adherence of the Hycar 1072 coating to the lead
foil is secured when a small quantity of n-(trimethoxysilylpropyl)
ethylene diamine (produced and sold by Dow-Corning under the
trademark A-6020 Silane) is mixed with the Hycar 1072. This
additive assists the bonding, it is believed, by forming a chemical
linkage with the lead surface.
FIG. 8 shows a container C' of the invention positioned between two
sheets of a photographic film pack P within a camera 49. When pack
P is pulled out of the camera 49 between a pair of pressure rolls
51 after a picture has been taken, the rolls compress container C'
and burst the seal at the lagging edge thereof, thus causing the
photographic processing solution to be expelled and distributed
uniformly into contact with the photographic emulsion on the
photographically exposed sheet of pack P. Reference is made to U.S.
Pat. No. 3,294,538 for further description of such a camera. It is
evident that similar results can be secured by passing a pair of
rolls across a stationary container C'.
The invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
* * * * *